Abstract:

Disclosed is the use of an aqueous dispersion comprising (a) a micronized
sparingly soluble organic benzophenone derivative of formula (1),
selected from the crystal modifications (B) and (C), wherein the crystal
modification (B) is characterized by a peak in the X-ray diffraction
pattern at a d-spacing of about 7.70; and wherein the crystal
modification (C) is characterized by a peak in the X-ray diffraction
pattern at a d-spacing of about 7.06; and (b) a dispersing agent selected
from anionic, non-ionic and amphoteric surfactants; for protecting the
human skin from browning and skin aging. The new crystal modification (C)
represents a thermodynamically stable compound of formula (1) at
25° C. This modification is therefore suitable in dispersions
comprising micro-fine particles.
##STR00001##

Claims:

1. A method for protecting the human skin from browning and skin aging
comprisingapplying to said skin an aqueous dispersion comprising(a) a
micronized sparingly soluble organic benzophenone derivative of formula
##STR00018## selected from the crystal modifications (B) and (C),wherein
the crystal modification (B) is characterized by a peak in the X-ray
diffraction pattern at a d-spacing of about 7.70 Å; andwherein the
crystal modification (C) is characterized by a peak in the X-ray
diffraction pattern at a d-spacing of about 7.06 Å; and(b) a
dispersing agent selected from anionic, non-ionic and amphoteric
surfactants.

2. The method according to claim 1, wherein(B) is characterized by peaks
at d-spacings of about 4.29, 5.36 und 7.70 Å.

3. The method according to claim 1, wherein(B) is characterized by peaks
at d-spacings of about 3.81, 4.29, 4.84, 5.36, 5.58, 7.28, 7.70 und 8.54
Å.

Description:

[0001]The present invention relates to the use of specific transmission
dyes for protecting human hair and skin against UV radiation and skin
aging and preventing tanning and cosmetic or dermatological compositions
comprising these dyes.

selected from the crystal modifications (B) and (C), [0007]wherein the
crystal modification (B) is characterized by a peak in the X-ray
diffraction pattern at a d-spacing of about 7.70 Å; and [0008]wherein
the crystal modification (C) is characterized by a peak in the X-ray
diffraction pattern at a d-spacing of about 7.06 Å; and(b) a
dispersing agent selected from anionic, non-ionic and amphoteric
surfactants; for protecting the human skin from browning and skin aging.

[0012]In addition X-ray diffraction data of a single-crystal of the new
modification (B) are recorded on a Nonius-Kappa-CCD using Mo X-rays
[λ(MoK.sub.α)=0.71073 Å] at 200K. The unit cell and the
crystal structure are determined with these data.

[0013]The crystal used has the following dimensions:
0.15×0.09×0.04 mm.

[0014]The basic crystallographic data (diffraction on single crystal) for
the new crystal modification (B) of compound of formula (1) are shown in
Table 2:

[0018]The compounds of formula (1) may be prepared according to known
methods as described for example in EP-1,046,391 or WO 04/052837.

[0019]The crystal modification (B) of formula (1) is obtained by
dissolving the compound of formula (1), prepared according to known
methods, in acetonitrile by heating to the boiling point and cooling down
to 25° C. with a exponential descending temperature profile.

[0020]The crystal modification (C) of formula (1) is obtained by
elutriation of the compound of formula (1) in N-methylpyrrolidone at
25° C. and stirring the suspension for about three days at
25° C.

[0021]Alternatively, the crystal modifications (C) of formula (1) is
obtained by elutriation of the crystal modifications (B) of formula (1)
in N-methylpyrrolidone or in other solvents or in mixtures of these at
temperatures between 0 and 50° C. and stirring the suspension for
about three days.

[0022]The crystal modifications (B) and (C) of the compound of formula (1)
according to the present invention are sparingly soluble organic
compounds which are preferably used in the present invention in the
micronized state. The preparation of micronized particles may be carried
out by any known processes, for example wet-milling, wet-kneading,
spray-drying from a suitable solvent, by expansion according to the RESS
process (Rapid Expansion of Supercritical Solutions) of supercritical
fluids (e.g. CO2, by reprecipitation from suitable solvents,
including supercritical fluids (GASR process=Gas Anti-Solvent
Recrystallisation/PCA process=Precipitation with Compressed
Anti-solvents)).

[0023]As milling apparatus for the preparation of the sparingly soluble
micronized organic compounds there may be used, for example, a jet mill,
ball mill, vibratory mill or hammer mill, preferably a high-speed mixing
mill. Even more preferable mills are modern ball mills; manufacturers of
these types of mill are, for example, Netzsch (LMZ mill), Drais
(DCP-Viscoflow or Cosmo), Buhler AG (centrifugal mills) or Bachhofen.

[0024]Examples of kneading apparatus for the preparation of the micronised
organic UV absorbers are typical sigma-blade batch kneaders but also
serial batch kneaders (IKA-Werke) or continuous kneaders (Continua from
Werner and Pfleiderer).

[0025]The grinding of the sparingly soluble organic compounds used in the
present invention is preferably carried out with a grinding aid.

[0026]The dispersing agent (b) is used as a low molecular weight grinding
aid for all the above micronisation processes.

[0034]The specific dispersing agents may be used in an amount of, for
example, from 1 to 30% by weight, especially from 2 to 20% by weight and
preferably from 3 to 10% by weight, based on the total weight of the
composition.

[0036]The micronised sparingly soluble organic compounds so obtained
usually have an average particle size from 0.02 to 2 micrometres,
preferably from 0.03 to 1.5 micrometres and more especially from 0.05 to
1.0 micrometres.

[0047]The cosmetic or pharmaceutical preparations can be prepared by
physically mixing the UV absorber(s) with the adjuvant using customary
methods, for example by simply stirring together the individual
components, especially by making use of the dissolution properties of
already known cosmetic UV absorbers, like octyl methoxy cinnamate,
salicylic acid isooctyl ester, etc. The UV absorber can be used, for
example, without further treatment, or in the micronised state, or in the
form of a powder.

[0048]Cosmetic or pharmaceutical preparations contain from 0.05-40% by
weight, based on the total weight of the composition, of one UV absorber
or UV absorber mixtures.

[0049]Preference is given to the use of mixing ratios of the compound of
formula (1) according to the present invention and optionally further
light-protective agents from 1:99 to 99:1, preferably from 5:95 to 95:5
and most preferably from 10:90 to 90:10, based on weight. Of special
interest are mixing ratios of from 20:80 to 80:20, preferably from 40:60
to 60:40 and most preferably approximately 50:50. Such mixtures can be
used, inter alia, to improve the solubility or to increase UV absorption.

[0050]The compounds of formula (1) may also be used as an anti-wrinkle
perception modifier.

[0051]This is a further object of the present invention.

[0052]The cosmetic or pharmaceutical preparations may be, for example,
creams, gels, lotions, alcoholic and aqueous/alcoholic solutions,
emulsions, wax/fat compositions, stick preparations, powders or
ointments. In addition to the above mentioned UV filters, the cosmetic or
pharmaceutical preparations may contain further adjuvants as described
below.

[0053]As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and
W/O/W emulsions or microemulsions) the preparations contain, for example,
from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and
especially from 0.5 to 10% by weight, based on the total weight of the
composition, of one or more UV absorbers, from 1 to 60% by weight,
especially from 5 to 50% by weight and preferably from 10 to 35% by
weight, based on the total weight of the composition, of at least one oil
component, from 0 to 30% by weight, especially from 1 to 30% by weight
and preferably from 4 to 20% by weight, based on the total weight of the
composition, of at least one emulsifier, from 10 to 90% by weight,
especially from 30 to 90% by weight, based on the total weight of the
composition, of water, and from 0 to 88.9% by weight, especially from 1
to 50% by weight, of further cosmetically acceptable adjuvants.

[0056]The final formulations listed may exist in a wide variety of
presentation forms, for example: [0057]in the form of liquid
preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of
microemulsions, [0058]in the form of a gel, [0059]in the form of an oil,
a cream, milk or lotion, [0060]in the form of a powder, a lacquer, a
tablet or make-up, [0061]in the form of a stick, [0062]in the form of a
spray (spray with propellent gas or pump-action spray) or an aerosol,
[0063]in the form of a foam, or [0064]in the form of a paste.

[0065]Of special importance as cosmetic preparations for the skin are
light-protective preparations, such as sun milks, lotions, creams, oils,
sunblocks or tropicals, pretanning preparations or after-sun
preparations, also skin-tanning preparations, for example self-tanning
creams. Of particular interest are sun protection creams, sun protection
lotions, sun protection milk and sun protection preparations in the form
of a spray.

[0079]5 g of the compound of formula (101) are dissolved in acetonitrile
by heating to the boiling point.

[0080]The solution is cooled down to 25° C. with an exponential
descending temperature profile of 80 C.°.

[0081]The obtained crystals are filtered off, washed twice with 10 g water
each and dried in a vacuum drying cabinet.

[0082]FIG. 1 shows the powder X-ray diffraction pattern of modification
(B), obtained from example A2; the values are given in 2θ. The
characteristic d-spacings of modification (B) are listed in Table 1.

Example A3

Preparation of Modification (C)

Example A3.1

[0083]5 g of the compound obtained in Example A2 (modification (B)) are
elutriated in 50 g N-methylpyrrolidone at 25 C.

[0084]The suspension is stirred for 3 days at 25 C.

[0085]The crystals are filtered off, washed twice with water and dried in
a vacuum drying cabinet at 50 C.

Example A3.2

[0086]5 g of the compound of formula (1) obtained in Example A1 are
elutriated in 50 g 2-butanone at 25 C.

[0087]The suspension is stirred for 3 days at 25 C.

[0088]The crystals are filtered off, washed twice with water and dried in
a vacuum drying cabinet at 50 C.

[0089]FIG. 2 shows the powder X-ray diffraction pattern of modification
(C), obtained from example A3.2; the values are given in 2θ.

[0102]Part A by is prepared by incorporating all ingredients, then stirred
under moderate speed and heated to 75° C. Part B is prepared and
heated to 75° C. At this temperature part B is poured into part A
under progressive stirring speed. Then the mixture is homogenized (30
sec., 15000 rpm). At a temperature <55° C. the ingredients of
part C are incorporated. The mixture is cooled down under moderate
stirring, then the pH is checked and adjusted with triethanolamine.

[0104]Part A is prepared by incorporating all ingredients, then stirred
under moderate speed and heated to 75° C. Part B is prepared and
heated to 75° C. At this temperature, part B is poured into part A
under progressive stirring speed. Below 65° C. the ingredients of
part D are added separately. After cooling down under moderate stirring
to 55° C. part C is added. The pH is then checked and adjusted
with sodium hydroxide. The mixture is homogenized for 30 sec at 16000
rpm.

[0106]Part A is prepared by incorporating all ingredients, then stirred
under moderate speed and heated to 75° C. Part C is prepared and
heated to 75° C. Part C is poured into the part A under moderate
stirring. Immediately after the emulsification part B is added, then
neutralized with a part of the triethanolamine. The mixture is
homogenized for 30 sec. After cooling down under moderate stirring
Cyclopentasiloxane (and) Dimethiconol are added. Below 35° C. the
pH is checked and adjusted with triethanolamine.

[0108]Part A and part B are heated up to 80° C. Part A is blended
into part B under stirring and homogenized with an UltraTurrax at 11 000
rpm for 30 sec. Part C is heated to 60° C. and added slowly to the
emulsion. After cooling down to 40° C. part D is incorporated at
room temperature and part E is added.

[0110]Part A and B are heated to 75° C. Part A is added into part B
under continuous stirring and homogenized with 11000 rpm for 1 minute.
After cooling down to 50° C. part C is added under continuous
stirring. After cooling further down to 30° C. part D is added.
Afterwards the pH is adjusted between 6.00-6.50.

[0112]Part A and B are heated separately to 75° C. After adding
part B into part A the mixture is homogenized with Ultra Turrax for one
minute at 11000 rpm. After cooling down to 50° C. part C is added.
Afterwards the mixture is homogenized for one minute at 16000 rpm. At a
temperature <40° C. part D is added. At room temperature the
pH-value is adjusted with part E between 6.00 and 6.50.

[0114]Part A and B are heated separately up to 75° C., part C is
heated to 60° C. Afterwards part B is poured into part A under
stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at
11 000 rpm and part C is incorporated. After cooling down to 40°
C. part D is added. At room temperature the pH-value is adjusted with
Sodium Hydroxide between 6.30 and 6.70 and part F is added.

[0116]Part A and B are heated separately up to 75° C., part C is
heated to 60° C. Afterwards part B is poured into part A under
stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at
11 000 rpm and part C is incorporated. After cooling down to 40°
C. part D is added. At room temperature the pH-value is adjusted with
Sodium Hydroxide between 6.30 and 6.70 and part F is added.

[0118]Part A and part B are heated separately to 75° C. Part B is
added into part A under continuous stirring and afterwards homogenized
with Ultra Turrax for 30 sec at 11000 rpm. After cooling down to
60° C. part C is added. At 40° C. part C is added and
homogenized for 15 sec at 11000 rpm. At room temperature the pH-value is
adjusted with part E.

[0120]Part A and B are heated separately to 75° C.; part C to
60° C. Part B is poured into part A under stirring. After
one-minute of homogenization at 11000 rpm part C is added to the mixture
of A/B. After cooling down to 40° C. part D is incorporated. At
room temperature the pH value is adjusted with part E between 6.3 and
7.0. Finally part F is added.

[0122]Part A and part B are heated separately to 75° C. Part A is
poured into part B under stirring. Immediately after the emulsification,
part C is added to the mixture and homogenized with an Ultra Turrax at
11000 rpm for 30 sec. After cooling down to 65° C. Sodium
Acrylates Copolymer (and) Mineral Oil (and) PPG-1 Trideceth-6 At
50° C. is added slowly to the UV absorber dispersion. At about
35-30° C. part F is incorporated. The pH is adjusted with part G
between 5.5 and 6.5.

[0124]Part A and part B are heated separately up to 80° C. Part A
is poured into part B while stirring and homogenized with an Ultra Turrax
by 11000 rpm for 30 sec. After cooling down to 60° C. part C is
incorporated. At 40° C. part D is added slowly under continuous
stirring. The pH is adjusted with part E between 6.50-7.00.

[0126]Part A and part B are heated separately up to 80° C., part C
is heated to 50° C. Part B is poured into part A and homogenized
with an Ultra Turrax for 1 minute at 11000 rpm. After cooling down to
50° C. part C is added under continuous stirring. At 40° C.
part D is incorporated and homogenized again for 10 sec. at 11000 rpm.
The pH is adjusted with part E.

[0128]Part A and part B are heated separately up to 75° C., part C
is heated to 60° C. Afterwards part B is poured into part A under
stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at
11 000 rpm and part C is incorporated. After cooling down to 40°
C. part D is added. At room temperature the pH-value is adjusted with
Sodium Hydroxide between 6.30 and 6.70 and part F is added.

[0130]Part A and part B are heated separately to 80° C. Part A is
poured into part B under continuous stirring. Afterwards the mixture is
homogenized with an Ultra Turrax at 11 000 rpm for 1 min. After cooling
down to 60° C. part C is incorporated. At 40° C. part D is
added and the mixture homogenized for a short time again. At 35°
C. part E is added and at room temperature Fragrance is added. Finally
the pH is adjusted with Sodium Hydroxide.

[0132]Part A and part B are heated separately up to 80° C. Part B
is poured into part A under moderate stirring. The mixture is homogenized
with an Ultra Turrax at 11000 rpm for 1 minute. After cooling down to
70° C. part C is added under stirring. After cooling further down
to 50° C. part D is incorporated very slowly. At 40° C.
part E is added. At room temperature the pH adjusted with part F to 7.00
and part G is added.

[0134]Part A and part B are heated separately up to 80° C. Part B
is poured into part A under moderate stirring. The mixture is homogenized
with an Ultra Turrax at 11000 rpm for 1 minute. After cooling down to
70° C. add part C is added under stirring. After cooling further
down to 50° C. part D is incorporated very slowly. At 40°
C. part E is added. At room temperature the pH is adjusted with part F to
7.00 and part G is added.

[0136]Part A and part B are heated separately up to 75° C. Part B
is poured into part A under progressive stirring speed. At a temperature
<65° C. the ingredients of part D are added separately. After
cooling down to 55° C. under moderate stirring part C is added. At
a temperature <35° C. the pH is checked and adjusted with
Sodium Hydroxide and homogenized with an Ultra Turrax for 30 sec. at 11
000 rpm. At room temperature part F is added.

[0140]Part A is heated separately to 80° C. under gentle stirring.
Part B is added to part A and homogenized for one minute at 11000 rpm.
After cooling down to 30° C. part C is added under continuous
stirring.

[0142]This Sunscreen may also be used as an anti-wrinkle perception
modifier.

Manufacturing Instruction

[0143]Mix part A and heat up from 60 to 65° C. and add Disp. Slowly
under fast stirringAdd part B under moderate stirring at 60° C.Add
part B into part A under stirring at 60° C. to 75° C.Add
part C under stirring until homogenization (emulsification at fast
stirring, may be with ultra turrax)Add part D under moderate stirring
(60° C.)Finally add part E under stirring (60° C.) and cool
down under moderate stirring